scholarly journals Chiral control of spin-crossover dynamics in Fe(II) complexes

Author(s):  
Malte Oppermann ◽  
Francesco Zinna ◽  
Jérôme Lacour ◽  
Majed Chergui

Iron-based spin-crossover (SCO) complexes hold tremendous promise as multifunctional switches in molecular devices. However, real-world technological applications require the excited high-spin (HS) state to be kinetically stable – a feature that has only been achieved at cryogenic temperatures in the light-induced excited spin-state trapping effect. Here we demonstrate HS state trapping by controlling the chiral configuration of FeII(4,4’-dimethyl-2,2’-bipyridine)3 in solution, associated for stereocontrol with enantiopure ∆- or Λ-TRISPHAT anions. We characterize the HS state relaxation using a newly developed ultrafast circular dichroism technique in combination with transient absorption and anisotropy measurements. We find that the decay of the HS state is accompanied by ultrafast changes of its optical activity, reflecting the coupling to a symmetry-breaking torsional twisting mode, contrary to the commonly assumed picture. Furthermore, we show that the diastereoselective ion-pairing with the enantiopure anions suppresses the vibrational population of the identified twisting mode, thereby achieving a four-fold extension of the HS lifetime. Transferred to the solid state, this novel strategy may thus significantly improve the kinetic stability of iron(II)-based magnetic switches at room temperature.

2015 ◽  
Vol 127 (44) ◽  
pp. 13168-13172 ◽  
Author(s):  
Benedikt Rösner ◽  
Magdalena Milek ◽  
Alexander Witt ◽  
Benoît Gobaut ◽  
Piero Torelli ◽  
...  

2015 ◽  
Vol 54 (44) ◽  
pp. 12976-12980 ◽  
Author(s):  
Benedikt Rösner ◽  
Magdalena Milek ◽  
Alexander Witt ◽  
Benoît Gobaut ◽  
Piero Torelli ◽  
...  

2019 ◽  
Vol 572 ◽  
pp. 158-167 ◽  
Author(s):  
Wenfeng Han ◽  
Lingyu Wang ◽  
Zhi Li ◽  
Haodong Tang ◽  
Ying Li ◽  
...  

Author(s):  
K. A. Fisher ◽  
M. G. L. Gustafsson ◽  
M. B. Shattuck ◽  
J. Clarke

The atomic force microscope (AFM) is capable of imaging electrically conductive and non-conductive surfaces at atomic resolution. When used to image biological samples, however, lateral resolution is often limited to nanometer levels, due primarily to AFM tip/sample interactions. Several approaches to immobilize and stabilize soft or flexible molecules for AFM have been examined, notably, tethering coating, and freezing. Although each approach has its advantages and disadvantages, rapid freezing techniques have the special advantage of avoiding chemical perturbation, and minimizing physical disruption of the sample. Scanning with an AFM at cryogenic temperatures has the potential to image frozen biomolecules at high resolution. We have constructed a force microscope capable of operating immersed in liquid n-pentane and have tested its performance at room temperature with carbon and metal-coated samples, and at 143° K with uncoated ferritin and purple membrane (PM).


1993 ◽  
Vol 329 ◽  
Author(s):  
Michael Canva ◽  
Patrick Georges ◽  
Jean-Fran^ois Perelgritz ◽  
Alain Brun ◽  
Fréddric Chaput ◽  
...  

AbstractPhotoresistant laser dyes were trapped in silica based xerogel host matrices to obtain solid state tunable lasers. For this purpose very dense xerogel samples with improved chemical and physical properties were prepared at room temperature by the sol-gel technology. The as-prepared materials were polished to obtain optical quality surfaces and were used as new lasing media.Lasing action of such different dyes as rhodamine, perylene and pyrromethene doping dense sol-gel matrices was demonstrated. Efficiencies of 30 % or lifetimes of more than 100,000 shots were achieved with different new ≤dye dopant/host matrix≥ couples. Their different performances are reviewed and discussed.


2019 ◽  
Author(s):  
Meifeng Wang ◽  
Liyin Zhang ◽  
Yiqun Li ◽  
Liuqun Gu

<p></p>Anomerization of glycosides were rarely performed under basic condition due to lack of efficiency. Here an imidazole promoted anomerization of β-D-glucose pentaacetate was developed; and reaction could proceed in both organic solvents and solid state at room temperature. Although mechanism is not yet clear, this unprecedent mild anomerization in solid state may open a new promising way for stereoseletive anomerization of broad glucosides and materials design in the future..


1987 ◽  
Vol 52 (5) ◽  
pp. 1356-1361
Author(s):  
S. Abdel Rahman ◽  
M. Elsafty ◽  
A. Hattaba

The conformation of elastin-like peptides Boc-Ala-Pro-Gly-Val-APEGM, Boc-Ala-Pro-Gly-Val-Gly-Val-APEGM, Boc-Ala-Pro-Gly-Val-Ala-Pro-Gly-Val-Gly-Val-APEGM, Boc-Ala-Pro-Gly-Val-Gly-Val-Ala-Pro-Gly-Val-Gly-Val-APEGM were examined in solution using circular dichroism at 30 °C, 50 °C, and 70 °C and in solid state by IR at room temperature. The studies show that the β-turn is a significant conformational feature for peptides under investigation in solution at 30 °C and 50 °C, but at 70 °C the tetra, hexa, and decapeptides show the CD feature characteristic of the β-structure while the dodecapeptide spectra show the presence of β-turn which indicates the stability of the β-turn at this chain length. The IR spectra show that in the solid state at room temperature all investigated peptides assume essentially a β-turn except the tetrapeptide which present evidence of antiparallel β-structure. The β-turn contribution in the IR spectra increases with the increase of the chain length of the peptide.


2020 ◽  
Vol 11 (47) ◽  
pp. 7497-7505
Author(s):  
Jiannan Cheng ◽  
Kai Tu ◽  
Enjie He ◽  
Jinying Wang ◽  
Lifen Zhang ◽  
...  

A novel strategy for preparing block copolymers with semifluorinated alternating copolymers as macroinitiators was established by photocontrolled iodine-mediated RDRP under irradiation with blue LED light at room temperature.


2021 ◽  
Author(s):  
Iurii Galadzhun ◽  
Rafal Kulmaczewski ◽  
Namrah Shahid ◽  
Oscar Cespedes ◽  
Mark J Howard ◽  
...  

[Fe(bpp)2][BF4]2 (bpp = 2,6-di{pyrazol-1-yl}pyridine) derivatives bearing a bent geometry of hexadec-1-ynyl or hexadecyl substituents pyrazole are isomorphous, and high-spin at room temperature. However, only the latter compound undergoes an abrupt,...


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